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1 Question 3.1: Arrange the following metals in the order in which they displace each other from the solution of their salts. Al, Cu, Fe, Mg and Zn The following is the order in which the given metals displace each other from the solution of their salts. Mg, Al, Zn, Fe, Cu Question 3.2: Given the standard electrode potentials, K + /K = 2.93V, Ag + /Ag = 0.80V, Hg 2+ /Hg = 0.79V Mg 2+ /Mg = 2.37 V, Cr 3+ /Cr = 0.74V Arrange these metals in their increasing order of reducing power. The lower the reduction potential, the higher is the reducing power. The given standard electrode potentials increase in the order of K + /K < Mg 2+ /Mg < Cr 3+ /Cr < Hg 2+ /Hg < Ag + /Ag. Hence, the reducing power of the given metals increases in the following order: Ag < Hg < Cr < Mg < K Question 3.3: Depict the galvanic cell in which the reaction Zn(s) + 2Ag + (aq) Zn 2+ (aq) + 2Ag(s) takes place. Further show: (i) Which of the electrode is negatively charged? (ii) The carriers of the current in the cell. (iii) Individual reaction at each electrode. The galvanic cell in which the given reaction takes place is depicted as: (i) Zn electrode (anode) is negatively charged. Page 1 of 25

2 (ii) Ions are carriers of current in the cell and in the external circuit, current will flow from silver to zinc. (iii) The reaction taking place at the anode is given by, The reaction taking place at the cathode is given by, Question 3.4: Calculate the standard cell potentials of galvanic cells in which the following reactions take place: (i) 2Cr(s) + 3Cd 2+ (aq) 2Cr 3+ (aq) + 3Cd (ii) Fe 2+ (aq) + Ag + (aq) Fe 3+ (aq) + Ag(s) Calculate the r G θ and equilibrium constant of the reactions. (i) The galvanic cell of the given reaction is depicted as: Now, the standard cell potential is In the given equation, n = 6 F = C mol 1 = V Then, = C mol V Page 2 of 25

3 = CV mol 1 = J mol 1 = kj mol 1 Again, = RT ln K = K = antilog (34.496) = (ii) The galvanic cell of the given reaction is depicted as: Now, the standard cell potential is Here, n = 1. Then, = C mol V = J mol 1 = 2.89 kj mol 1 Again, Page 3 of 25

4 = K = antilog (0.5073) = 3.2 (approximately) Question 3.5: Write the Nernst equation and emf of the following cells at 298 K: (i) Mg(s) Mg 2+ (0.001M) Cu 2+ ( M) Cu(s) (ii) Fe(s) Fe 2+ (0.001M) H + (1M) H 2 (g)(1bar) Pt(s) (iii) Sn(s) Sn 2+ (0.050 M) H + (0.020 M) H 2 (g) (1 bar) Pt(s) (iv) Pt(s) Br 2 (l) Br (0.010 M) H + (0.030 M) H 2 (g) (1 bar) Pt(s). (i) For the given reaction, the Nernst equation can be given as: = = 2.67 V (approximately) (ii) For the given reaction, the Nernst equation can be given as: = V = 0.53 V (approximately) Page 4 of 25

5 (iii) For the given reaction, the Nernst equation can be given as: = log125 = = V = 0.08 V (approximately) (iv) For the given reaction, the Nernst equation can be given as: Question 3.6: In the button cells widely used in watches and other devices the following reaction takes place: Zn(s) + Ag 2 O(s) + H 2 O(l) Zn 2+ (aq) + 2Ag(s) + 2OH (aq) Determine and for the reaction. Page 5 of 25

6 = V We know that, = = J = kj Question 3.7: Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation with concentration. Conductivity of a solution is defined as the conductance of a solution of 1 cm in length and area of cross-section 1 sq. cm. The inverse of resistivity is called conductivity or specific conductance. It is represented by the symbolκ. If ρ is resistivity, then we can write: The conductivity of a solution at any given concentration is the conductance (G) of one unit volume of solution kept between two platinum electrodes with the unit area of cross-section and at a distance of unit length. i.e., (Since a = 1, l = 1) Conductivity always decreases with a decrease in concentration, both for weak and strong electrolytes. This is because the number of ions per unit volume that carry the current in a solution decreases with a decrease in concentration. Molar conductivity: Page 6 of 25

7 Molar conductivity of a solution at a given concentration is the conductance of volume V of a solution containing 1 mole of the electrolyte kept between two electrodes with the area of cross-section A and distance of unit length. Now, l = 1 and A = V (volume containing 1 mole of the electrolyte). Molar conductivity increases with a decrease in concentration. This is because the total volume V of the solution containing one mole of the electrolyte increases on dilution. The variation of with for strong and weak electrolytes is shown in the following plot: Question 3.8: The conductivity of 0.20 M solution of KCl at 298 K is Scm 1. Calculate its molar conductivity. Given, κ = S cm 1 c = 0.20 M Molar conductivity, = 124 Scm 2 mol 1 Page 7 of 25

8 Question 3.9: The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 Ω. What is the cell constant if conductivity of 0.001M KCl solution at 298 K is S cm 1. Given, Conductivity, κ = S cm 1 Resistance, R = 1500 Ω Cell constant = κ R = = cm 1 Question 3.10: The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results are given below: Concentration/M κ/s m Calculate for all concentrations and draw a plot between and c½. Find the value of. Given, κ = S m 1, c = M Then, κ = S cm 1, c½ = M 1/2 = S cm 2 mol 1 Given, κ = S m 1, c = 0.010M Then, κ = S cm 1, c½ = 0.1 M 1/2 Page 8 of 25

9 = S cm 2 mol 1 Given, κ = S m 1, c = M Then, κ = S cm 1, c 1/2 = M 1/2 = S cm 2 mol 1 Given, κ = S m 1, c = M Then, κ = S cm 1, c 1/2 = M 1/2 = S cm 2 mol 1 Given, κ = S m 1, c = M Then, κ = S cm 1, c 1/2 = M 1/2 = S cm 2 mol 1 Now, we have the following data: Page 9 of 25

10 Since the line interrupts at S cm 2 mol 1, = S cm 2 mol 1. Question 3.11: Conductivity of M acetic acid is S cm 1. Calculate its molar conductivity and if for acetic acid is S cm 2 mol 1, what is its dissociation constant? Given, κ = S m 1 c = mol L 1 Then, molar conductivity, = 32.76S cm 2 mol 1 Again, = S cm 2 mol 1 Now, Page 10 of 25

11 = Dissociation constant, = mol L 1 Question 3.12: How much charge is required for the following reductions: (i) 1 mol of Al 3+ to Al. (ii) 1 mol of Cu 2+ to Cu. (iii) 1 mol of to Mn 2+. (i) Required charge = 3 F = C = C (ii) Required charge = 2 F = C = C (iii) i.e., Required charge = 5 F = C = C Question 3.13: How much electricity in terms of Faraday is required to produce (i) 20.0 g of Ca from molten CaCl 2. Page 11 of 25

12 (ii) 40.0 g of Al from molten Al 2 O 3. (i) According to the question, Electricity required to produce 40 g of calcium = 2 F Therefore, electricity required to produce 20 g of calcium = 1 F (ii) According to the question, Electricity required to produce 27 g of Al = 3 F Therefore, electricity required to produce 40 g of Al = 4.44 F Question 3.14: How much electricity is required in coulomb for the oxidation of (i) 1 mol of H 2 O to O 2. (ii) 1 mol of FeO to Fe 2 O 3. (i) According to the question, Now, we can write: Electricity required for the oxidation of 1 mol of H 2 O to O 2 = 2 F = C = C (ii) According to the question, Page 12 of 25

13 Electricity required for the oxidation of 1 mol of FeO to Fe 2 O 3 = 1 F = C Question 3.15: A solution of Ni(NO 3 ) 2 is electrolysed between platinum electrodes using a current of 5 amperes for 20 minutes. What mass of Ni is deposited at the cathode? Given, Current = 5A Time = = 1200 s Charge = current time = = 6000 C According to the reaction, Nickel deposited by C = g Therefore, nickel deposited by 6000 C = g Hence, g of nickel will be deposited at the cathode. Question 3.16: Three electrolytic cells A,B,C containing solutions of ZnSO 4, AgNO 3 and CuSO 4, respectively are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? What mass of copper and zinc were deposited? According to the reaction: Page 13 of 25

14 i.e., 108 g of Ag is deposited by C. Therefore, 1.45 g of Ag is deposited by = = C Given, Current = 1.5 A Time = s = 864 s = min Again, i.e., C of charge deposit = 63.5 g of Cu Therefore, C of charge will deposit = g of Cu i.e., C of charge deposit = 65.4 g of Zn Therefore, C of charge will deposit = g of Zn Question 3.17: Using the standard electrode potentials given in Table 3.1, predict if the reaction between the following is feasible: (i) Fe 3+ (aq) and I (aq) Page 14 of 25

15 (ii) Ag + (aq) and Cu(s) (iii) Fe 3+ (aq) and Br (aq) (iv) Ag(s) and Fe 3+ (aq) (v) Br 2 (aq) and Fe 2+ (aq). Since feasible. for the overall reaction is positive, the reaction between Fe 3+ (aq) and I (aq) is Since feasible. for the overall reaction is positive, the reaction between Ag + (aq) and Cu (s) is Since for the overall reaction is negative, the reaction between Fe 3+ (aq) and Br (aq) is not feasible. Since not feasible. E for the overall reaction is negative, the reaction between Ag (s) and Fe 3+ (aq) is Page 15 of 25

16 Since for the overall reaction is positive, the reaction between Br 2(aq) and Fe 2+ (aq) is feasible. Question 3.18: Predict the products of electrolysis in each of the following: (i) An aqueous solution of AgNO 3 with silver electrodes. (ii) An aqueous solution of AgNO 3 with platinum electrodes. (iii) A dilute solution of H 2 SO 4 with platinum electrodes. (iv) An aqueous solution of CuCl 2 with platinum electrodes. (i) At cathode: The following reduction reactions compete to take place at the cathode. The reaction with a higher value of of silver will take place at the cathode. At anode: takes place at the cathode. Therefore, deposition The Ag anode is attacked by ions. Therefore, the silver electrode at the anode dissolves in the solution to form Ag +. (ii) At cathode: The following reduction reactions compete to take place at the cathode. Page 16 of 25

17 The reaction with a higher value of of silver will take place at the cathode. At anode: takes place at the cathode. Therefore, deposition Since Pt electrodes are inert, the anode is not attacked by ions. Therefore, OH or ions can be oxidized at the anode. But OH ions having a lower discharge potential and get preference and decompose to liberate O 2. (iii) At the cathode, the following reduction reaction occurs to produce H 2 gas. At the anode, the following processes are possible. For dilute sulphuric acid, reaction (i) is preferred to produce O 2 gas. But for concentrated sulphuric acid, reaction (ii) occurs. (iv) At cathode: The following reduction reactions compete to take place at the cathode. The reaction with a higher value of takes place at the cathode. Therefore, deposition of copper will take place at the cathode. At anode: The following oxidation reactions are possible at the anode. At the anode, the reaction with a lower value of is preferred. But due to the overpotential of oxygen, Cl gets oxidized at the anode to produce Cl 2 gas. Page 17 of 25

18 Text solution Question 3.1: How would you determine the standard electrode potential of the systemmg 2+ Mg? The standard electrode potential of Mg 2+ Mg can be measured with respect to the standard hydrogen electrode, represented by Pt (s), H 2(g) (1 atm) H + (aq)(1 M). A cell, consisting of Mg MgSO 4 (aq 1 M) as the anode and the standard hydrogen electrode as the cathode, is set up. Then, the emf of the cell is measured and this measured emf is the standard electrode potential of the magnesium electrode. Here, for the standard hydrogen electrode is zero. Page 18 of 25

19 Question 3.2: Can you store copper sulphate solutions in a zinc pot? Zinc is more reactive than copper. Therefore, zinc can displace copper from its salt solution. If copper sulphate solution is stored in a zinc pot, then zinc will displace copper from the copper sulphate solution. Hence, copper sulphate solution cannot be stored in a zinc pot. Question 3.3: Consult the table of standard electrode potentials and suggest three substances that can oxidise ferrous ions under suitable conditions. Substances that are stronger oxidising agents than ferrous ions can oxidise ferrous ions. ; = 0.77 V This implies that the substances having higher reduction potentials than V can oxidise ferrous ions to ferric ions. Three substances that can do so are F 2, Cl 2, and O 2. Question 3.4: Calculate the potential of hydrogen electrode in contact with a solution whose ph is 10. For hydrogen electrode,, it is given that ph = 10 [H + ] = M Now, using Nernst equation: = Page 19 of 25

20 = log = V Question 3.5: Calculate the emf of the cell in which the following reaction takes place: Given that = 1.05 V Applying Nernst equation we have: = log = (log log 4) = ( ) = V Question 3.6: The cell in which the following reactions occurs: Page 20 of 25

21 has = V at 298 K. Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction. Here, n = 2, We know that: T = 298 K = = J mol 1 = kj mol 1 Again, 2.303RT log K c = K c = Antilog (7.981) = Question 3.7: Why does the conductivity of a solution decrease with dilution? The conductivity of a solution is the conductance of ions present in a unit volume of the solution. The number of ions (responsible for carrying current) decreases when the solution is diluted. As a result, the conductivity of a solution decreases with dilution. Question 3.8: Suggest a way to determine the value of water. Page 21 of 25

22 Applying Kohlrausch s law of independent migration of ions, the be determined as follows: value of water can Hence, by knowing the values of HCl, NaOH, and NaCl, the value of water can be determined. Question 3.9: The molar conductivity of mol L 1 methanoic acid is 46.1 S cm2 mol 1. Calculate its degree of dissociation and dissociation constant. Given λ (H + ) = S cm 2 mol 1 and λ (HCOO ) = 54.6 S cm 2 mol C = mol L 1 Now, degree of dissociation: Thus, dissociation constant: Page 22 of 25

23 Question 3.10: If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would flow through the wire? I = 0.5 A t = 2 hours = s = 7200 s Thus, Q = It = 0.5 A 7200 s = 3600 C We know that Then, number of electrons. Hence, number of electrons will flow through the wire. Question 3.11: Suggest a list of metals that are extracted electrolytically. Metals that are on the top of the reactivity series such as sodium, potassium, calcium, lithium, magnesium, aluminium are extracted electrolytically. Question 3.12: What is the quantity of electricity in coulombs needed to reduce 1 mol of? Consider the reaction: Page 23 of 25

24 The given reaction is as follows: Therefore, to reduce 1 mole of =6 F = C = C, the required quantity of electricity will be: Question 3.14: Suggest two materials other than hydrogen that can be used as fuels in fuel cells. Methane and methanol can be used as fuels in fuel cells. Question 3.15: Explain how rusting of iron is envisaged as setting up of an electrochemical cell. In the process of corrosion, due to the presence of air and moisture, oxidation takes place at a particular spot of an object made of iron. That spot behaves as the anode. The reaction at the anode is given by, Electrons released at the anodic spot move through the metallic object and go to another spot of the object. There, in the presence of H + ions, the electrons reduce oxygen. This spot behaves as the cathode. These H + ions come either from H 2 CO 3, which are formed due to the dissolution of carbon dioxide from air into water or from the dissolution of other acidic oxides from the atmosphere in water. The reaction corresponding at the cathode is given by, The overall reaction is: Page 24 of 25

25 Also, ferrous ions are further oxidized by atmospheric oxygen to ferric ions. These ferric ions combine with moisture, present in the surroundings, to form hydrated ferric oxide i.e., rust. Hence, the rusting of iron is envisaged as the setting up of an electrochemical cell. Page 25 of 25

26 XO 2 = no 2 /(no 2+ n H 2O ) ~ = no 2 /nh 2O no 2 = 4.6 X 10-6 X 55.5 = 2.55 X 10-4 mol M = 2.55 X 10-4 M 16. Calculate the mass of compound (molarmass = 256 g/mol) to be dissolved in 75g of benzene to lower its freezing point by 0.48K(Kf =5.12K Kg/mol) CBSE Ans: Tf = Kf x W2 X1000/W1xM = 5.12xW2 x1000/75x256 W2 = 1.8g 17. Define an ideal solution and write one of its characteristics CBSE Ans. Ideal solution The solution which obeys Roult s law under all conditions of temperature and concentration and during the preparation of which there is no change in enthalpy and volume on mixing the component. Conditions P A = P 0 A X A, P B = P 0 B.X B H Mix = 0, V mix = 0 This is only possible if A-B interaction is same as A-A and B-B interaction nearly ideal solution are Molarity Density required Density required Molality Density not required Mole fraction CHAPTER-3 ELECTROCHEMISTRY

27 5 Marks Chapter Electrochemistry may be defined as the branch of chemistry which deals with the quantitative study of interrelation ship between chemical energy and electrical energy and interconversion of one form into another. A cell is of two types:- I. Galvanic Cell II. Electrolytic cell. In Galvanic cell the chemical energy of a spontaneous redox reaction is converted into electrical work. In Electrolytic cell electrical energy is used to carry out a non-spontaneous redox reaction. The Standard Electrode Potential for any electrode dipped in an appropriate solution is defined with respect to standard electrode potential of hydrogen electrode taken as zero. The standard potential of the cell can be obtained by taking the difference of the standard potentials of cathode and anode. E 0 cell = E 0 cathode-e 0 anode Concentration dependence of the potentials of the electrodes and the cells are given by Nernst equation. aa+bb cc + dd Nernst equation can be written as Ecell = E 0 cell-rt ln[c] c [D] d nf [A] a [B] b At 25 0C, Ecell = E 0 cell-0.059log [C] c [D] d n [A] a [B] b The standard potential of the cells are related of standard Gibbs energy. rg 0 =-nfe 0 cell

28 The standard Gibbs energy of the cells is related to equilibrium constant. rg 0 = -RTlnK The conductivity, K of an electrolytic solution depends on the concentration of the electrolyte, nature of solvent and temperature. Molar Conductivity, λm, is defined as the conductivity power of all the ions produced by one gram mole of an electrolyte in asolution. λm = K x 1000 Molarity(mol/L) Variation with dilution Conductivity(k) Molar conductivity Decreases Increases (Small increase in case of strong electrolytes) (Steep increase in case of weak electrolytes) Kohlrausch law of independent migration of ions. The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the individual contribution to the anion and cation of the electrolyte. Faraday s laws of Electrolysis I. The mass of any substance deposited or liberated at any electrode is directly proportional to the quantity of electricity passed through the electrolyte W = Z I t Mass(g) = Atomic wt. x I (Ampere) x t(s) x valency

29 II. The amount of different substances liberated by the same quantity of electricity passing through the electrolytic solution is proportional to their chemical equivalent weights. Batteries and full cells are very useful forms of galvanic cells There are mainly two types of batteries. i) Primary batteries eg: Dry cell, Mercury cell ii) Secondary batteries(rechargeable) eg: Lead storage battery, Nickel cadmium storage cell Corrosion of metals is an electrochemical phenomenon. In corrosion metal is oxidized by loss of electrons to oxygen and formation of oxides. Anode (Oxidation): 2Fe(s) 2Fe e - Cathode (Reduction): O2(g) + 4H + (aq) + 4e - 2H2O Atmospheric Oxidation: 2Fe 2+ (aq) + 2H2O(l) + 1/2O2(g) Fe2O3(s) + 4H + (aq) QUESTION CARRING 1 MARK 1. What is the effect of temperature on molar conductivity? Ans. Molar conductivity of an electrolyte increases with increase in temperature. 2. Why is it not possible to measure single electrode potential? Ans. It is not possible to measure single electrode potential because the half cell containing single electrode cannot exist independently, as charge cannot flow on its own in a single electrode. 3. Name the factor on which emf of a cell depends:- Ans. Emf of a cell depends on following factor- a. Nature of reactants. b. Concentration of solution in two half cells. c. Temperature d. Pressure of gas. 4. What are the units of molar conductivity? ( cm 2 ohm -1 mol -1 or Scm 2 mol -1)

30 5. Write Nernst equation For the general cell reaction aa+bb cc+dd Ans. Ecell = E 0 cell- RT ln[c] c [[D] d nf [A] a [B] b 6. What is the EMF of the cell when the cell reaction attains equilibrium? Ans. Zero 7. What is the electrolyte used in a dry cell? Ans. A paste of NH4Cl, MnO2 and C 8. How is cell constant calculated from conductance values? Ans. Cell constant= Resistance x Conductivity 9. What flows in the internal circuit of a galvanic cell. Ans. Ions 10. Define electrochemical series. Ans. The arrangement of various electrodes in the decreasing or increasing order of their standard reduction potentials is called electrochemical series. QUESTIONS CARRYING TWO MARKS 1. How can you increase the reduction potential of an electrode.? For the reaction M n+ (aq) + ne - - M (s) Ans. Nernst equation is: E M n+ /M = E 0 M n+ /M RT log 1

31 EM n+/m can be increased by nf [M n+ ] a. increase in concentration of M n+ ions in solution b. by decreasing the temperature. 2. Calculate emf of the following cell at 298K Zn/Zn 2+ (10-4 M) Cu 2+ (10-2 M)/Cu Given E 0 Zn 2+ /Zn=-0.76V E 0 Cu 2+ /Cu=+0.34V Ans. Cell reaction is as follows. Zn(s) + Cu 2+ (aq) Zn 2+ (aq) + Cu(s) No of electrons transfers (n)=2 T=298K Ecell=(E 0 Cu 2+ /Cu-E 0 Zn 2+ /Zn) log [Zn 2+ (aq)] 2 [Cu 2+ (aq)] = 0.34V-(-0.76) log10-4 = 1.10V V log 10-2 = 1.10V+2 X V = 1.10V V = V 10-2 Q 3. Electrolysis of KBr(aq) gives Br2 at anode but KF(aq) does not give F2. Give reason. Ans. Oxidation takes place at anode. Now higher the oxidation Potential, easier to oxidize. Oxidation potential of Br -, H2O, and F - are in the following order. Br->H2O>F-

32 Therefore in aq. Solution of KBr, Br - ions are oxidized to Br2 in preference to H2O. On the other hand, in aq. Solution of KF, H2O is oxidized in preference to F -. Thus in this case oxidation of H2O at anode gives O2 and no F2 is produced. 3. What happens when a piece of copper is added to (a) an aq solution of FeSO4(b) an Aq solution of FeCl3? a. Nothing will happen when the piece of copper is added to FeSo4 because reduction potential E 0 Cu 2+ /Cu(0.34) is more than the reduction potential E0(Fe2+/Fe) (0.44V). b. Copper will dissolve in an aq solution of FeCl3 because reduction potential E 0 Fe 3+ /Fe 2+ (0.77V) is more than the reduction potential of E 0 Cu 2+ /Cu(0.34) Cu(s)+ 2FeCl3 (aq) Cu 2+ (aq) + 2 FeCl2(aq) 4. Define corrosion. Write chemical formula of rust. Ans. Corrosion is a process of determination of metal as a result of its reaction with air and water, surrounding it. It is due to formulation of sulphides, oxides, carbonates, hydroxides, etc. Formula of rust- Fe2O.XH2O 5. What is cell constant? Ans. Ratio of distance between electrodes and cross section area of elecrode G* = l / A 6. Why mercury cell gives the constant voltage. Ans. Elecrolytes are not consuming during the reaction. 7. What is fuel cell, write reaction involved in H2-O2 fuel cell. QUESTION CARRYING THREE MARKS 1. Write any three differences between potential difference and e.m.f. E.M.F POTENTIAL DIFFERENCE 1.It is difference between electrode potential of two electrodes when no current is flowing through 1.it is difference of potential between electrode in a closed circuit. circuit.

33 2. it is the maximum voltage obtained 2.it is less than maximum voltage From a cell. Obtained from a cell. 3. it is responsible for steady flow of 3.it is not responsible for steady Current. Flow of current. 2. Why an electrochemical cell stops working after sometime? The reduction potential of an electrode depends upon the concentration of solution with which it is in contact. As the cell works, the concentration of reactants decrease. Then according to Le chatelier s principle it will shift the equilibrium in backward direction. On the other hand if the concentration is more on the reactant side then it will shift the equilibrium in forward direction. When cell works concentration in anodic compartment in cathodic compartment decrease and hence E 0 cathode will decrease. Now EMF of cell is E 0 cell= E 0 cathode E 0 anode A decrease in E 0 cathode and a corresponding increase in E 0 anode wil mean that EMF of the cell will decrease and will ultimately become zero i.e., cell stops working after some time. 3. For the standard cell Cu(s)/Cu + (aq) Ag + (aq)/ag(s) E 0 cell 2+/ Cu = V E 0 cell 2+ =+0.34 V E 0 Ag + /Ag =+0.80 V i. identify the cathode and the anode as the current is drawn from the cell. ii. Write the reaction taking place at the electrodes. iii. Calculate the standard cell potential. Ans. 1.From the cell representation

34 Ag/Ag + electrode is cathode and Cu/Cu + electrode is anode. 1. At anode : At Cathode : Cu(s) Cu 2+ ( aq )+2e - 2Ag+ + 2e 2Ag(s) E 0 cell = E 0 cathode E 0 anode = E 0 Ag+/Ag E 0 Cu2+ /Cu = +.80 V (+0.34V) = +0.80V-0.34V = 0.46V 2. Can we store copper sulphate in (i)zinc vessel (ii) Silver vessel? Give reasons. Given E 0 Cu 2+ /Cu = +0.34V, E 0 Zn 2+ /Zn= -0.76V), E0Ag + /Ag = +0.80V Ans. A metal having lower reduction potential can displace a metal having higher reduction potential from solution of its salt. I. Since standard reduction potential of Zn 2+ (E 0 Zn 2+ /Zn = -0.76V) is less than the standard reduction potentialof Cu 2+ (E 0 Cu 2+ /Cu=+0.34V), Zn can displace copper from copper sulphate solution but Ag cannot. Thus, CuSO4 solution can be stored in silver vessel. 3. How many grams of chlorine can be produced by the electrolysis of molten NaCl with a current of 1.02 A for 15 min? Mass(g) = Atomic wt. x I (Ampere) x t(s) x valency = 35.5 x 1.02 x 15 x x 1 = gm 4. Write the equation showing the effect of concentration on the electrode potential. 5. Derive the relationship between Gibb s free energy change and the cell potential.

35 6. How Nernst equation can be applied in the calculation of equilibrium constant of any cell reaction.? 7. The cell reaction as written is spontaneous if the overall EMF of the cell is positive. Comment on this statement. QUESTIONS CARRYING 5 MARKS 1. I) Define the following terms CBSE a) Limiting molar conductivity b) Fuel cell II) Resistance of a conductivity cell filled with 0.1 mol/l KCl solution is 100Ω. If the resistance of the same cell when filled with 0.02mol/L KCl solution is 520Ω. Calculate the conductivity and molar conductivity of 0.02mol/L KCl solution. The conductivity of 0.1 mol/l KCl solution is 1.29x10-2 Ω -1 cm -1 Ans. NCERT book Page No. 2. a) State Faraday s first law of electrolysis. How much charge in terms of Faraday is required for the reduction of 1 mol of Cu2+ to Cu. CBSE b) Calculate emf of the following cell at 298K. Mg(s)/Mg2+(0.1M)//Cu2+(0.01)/Cu Ans: a) Amount of substance deposited at an electrode is directly proportional to the quantity of electricity passed through the electrolyte. 2F B. Ecell = E0cell log[mg2+] n [Cu2+] = log[0.1] = 2.68V 2 [0.01] 3. Explain the term electrolysis. Discuss briefly the electrolysis of (i) molten NaCl (ii) aqueous sodium chloride solution (iii) molten lead bromide (iv) water. 4. state and explain Faraday s laws of electrolysis. What is Electrochemical equivalent? 5. What do you understand by electrolytic conduction? what are the factors on which electrolyte conduction depends.? What is the effect of temperature on electrolytic conduction? 6. How is electrolytic conductance measured experimentally? 7. Describe normal hydrogen electrode and its applications. 1 Mark questions:- HOT QUESTIONS 1. Why in a concentrated solution, a strong electrolyte shows deviations from Debye-Huckle- Onsagar equation?

36 Ans:- Because interionic forces of attractions are large. 2. What is the use of Platinum foil in the hydrogen electrode? A: It is used for inflow and outflow of electrons. 3. Corrosion of motor cars is of greater problem in winter when salts are spread on roads to melt ice and snow. Why? A: Salts in water are the better electrolytes. 4. Is it safe to stir AgNO3 solution with copper spoon? (E 0 Ag+/ Ag = 0.80 Volt; E 0 Cu+/ Cu = 0.34 Volt) Ans: No it is not safe because reacts with AgNO3 Solution ( emf will be positive.) 5. Why is it necessary to use salt bridge in A galvanic cell? Ans: To complete inner circuit and to maintain electrical neutrality of the solution. 2 mark questions:- 1. Why is Li best reducing agent where as Fluorine is best oxidizing agent? 2. Equilibrium constant is related to Eθ cell but not to Ecell. Explain. 3. Why sodium metal is not obtained at cathode when aq NaCl is electrolysed with Pt electrodes but obtained when molten NaCl is electrolysed? 2 4. Zn rod weighing 25 g was kept in 100 ml of 1M copper sulphate solution. After certain time interval, the molarity of Cu 2+ was found to be 0.8 M. What is the molarity of SO4-2 in the resulting solution and what should be the mass of Zn rod after cleaning and drying? 8. Which will have greater molar conductivity and why? Sol A. 1mol KCl dissolved in 200cc of the solution or Sol B. 1 mol KCl dissolved in 500cc of the solution. 9. Calculate the equilibrium constant for the reaction Zn + Cd 2+ Zn 2+ +Cd If E 0 Cd ++ /Cd =-.403 v E 0 Zn ++ /Zn= v 3/ 5 mark questions:- 1. What do you mean by ( i) negative standard electrode potential and (ii) positive standard electrode potential?

37 2. Which cell is generally used in hearing aids? Name the material of the anode, cathode and the electrolyte. Write the reactions involved. 3. Iron does not rust even if Zinc coating is broken in galvanized iron pipe but rusting occurs much faster if tin coating over iron is broken. Explain. 4. Corrosion is an electrochemical phenomenon, explain. 5. Calculate the ph of following cell: Pt, H2/ H2SO4, if its electrode potential is0.03v. 6. A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution of 10-5 M H+ ions. The emf of the cell is V at 298 K. Calculate the concentration of the H+ ions at the positive electrode. 7. Crude copper containing Fe and Ag as contaminations was subjected to electro refining by using a current of 175 A for min. The mass of anode was found to decrease by g, while that of cathode was increased by g. Estimate the % of copper, iron and silver in crude copper. 8 Zinc electrode is constituted at 298 K by placing Zn rod in 0.1 M aq solution of zinc sulphate which is 95 % dissociated at this concentration. What will be the electrode potential of the electrode given that EθZn2+/Zn= V At what ph will hydrogen electrode at 298 K show an electrode potential of V, when Hydrogen gas is bubbled at 1 atm pressure? 3 10 Electrolysis of the solution of MnSO4 in aq sulphuric acid is a method for the preparation of MnO2 as per the chemical reaction Mn2+ + 2H2O MnO2 + 2H+ + H2 Passing a current of 27 A for 24 Hrs gives 1 kg of MnO2. What is the current efficiency? What are the reactions occurring at anode and cathode? 11. What do you mean by kohlrauch s law: from the following molar conductivities at infinite dilution λ o m Ba(OH)2 =457.6 Ω -1 cm 2 mol -1 λ o m Ba Cl2 = Ω -1 cm 2 mol -1 λ o m NH4Cl= Ω -1 cm 2 mol -1

38 Calculate λ o m for NH4 OH CHAPTER-4 CHEMICAL KINETICS 5 Marks Chapter Key points